JPH0768335B2 - Functionalization of reactive surfaces - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to electronic packaging applications, and is commonly used as a substrate, especially in electronic packaging applications,
It relates to a method of functionalizing the surface of a dielectric polymer insulator to render the surface of a polymer substrate reactive, while leaving the overall properties of the substrate unchanged.

[0002]

BACKGROUND OF THE INVENTION For many electronic packaging applications, the use of certain polymeric materials as dielectric insulators has been found to have excellent overall properties (ie, dielectric constant, water absorption, thermal stability, mechanical stability). It is desirable because of the characteristics). In the past, we have encountered some difficulties related to the surface properties of these materials. Such difficulties include insufficient bond strength and bond durability and surface metallization and inability to inoculate.

One method for overcoming unwanted surface properties and maintaining a desirable overall strength of the substrate is to physically or chemically leave the overall properties of the material untouched. To change its surface either by the target.

Goldblatt et al., US Pat. No. 5,019,2
No. 10 discloses a method of treating a polymer surface with a plasma of water vapor to enhance the adhesion of the treated polymer surface to a second polymer surface. on the other hand,
The present invention involves treating the polymer surface with steam plasma, which renders the surface chemically reactive. The surface of this treated polymer is then treated with a selected composition that provides the desired layer on the surface.

There are many other known techniques that can be applied to functionalize the substrate surface.

US Pat. No. 3,676,19 to Landler et al.
No. 0 says that to form a substantially pure graft polymer, the polymer is exposed to ozone at a temperature not exceeding 130 ° C. to form an “ozonated” polymer, which is then reacted with an ethylenically unsaturated monomer. One method is disclosed. The ozone used in this known example is not equivalent to the water vapor plasma used in the present invention,
Also, the ethylenically unsaturated monomer of this example is not the same as the grafting agent component used in the present invention,
This known example is a method different from that embodied in the present invention.

US Pat. Nos. 3,759,954 and 3,
Nos. 879,422 and 3,956,317 all relate to diepoxide compositions and merely mention diepoxides and do not indicate the method embodied in the present invention.

US Pat. No. 4,078,09 to Redmond et al.
No. 6 pre-treats the substrate surface with a hydrazine solution, then deposits a catalyst on the surface-treated polymer, and a bath containing therein a metal capable of electroless deposition on the polymer containing the catalyst. It shows a method of forming a circuit pattern on a polyimide substrate by exposing a polymer having this catalyst to. This patent relates to inoculation and plating, but does not show the surface functionalization by steam plasma and the grafting agent component as embodied in the present invention.

US Pat. No. 4,400,424 to Hatada et al.
No. 1 relates to the dye sensitivities induced in textile fibers by forming recesses in the fibers and is only relevant to the area of use of cold plasma. The method presented here is not directly related to the present invention.

US Pat. No. 4,410,5 to Ladizescky et al.
No. 86 shows a method of making a composite of reinforcing materials such that the fibers are embedded in a matrix material. It is shown in this document that the material to be strengthened is plasma treated before it is placed in the matrix, preferably creating depressions in its surface, which results in compatibility of the adhesion with the matrix. . This document is also not relevant to the present invention.

US Pat. No. 4,637,851 to Ueno et al. Forms a pretreated textile sheet by exposing it to a low temperature plasma generated under reduced pressure in an atmosphere of a gas such as a mixture of oxygen and nitrogen. Discloses a method for preparing a prepreg laminate matrix. This document is also not relevant to the present invention.

Ueno et al., US Pat. No. 4,664,936, also discloses resin impregnated composite prepreg materials based on woven materials of aromatic polyamide fibers exposed to low temperature plasma. The patent states that the adhesive bond strength between the binder and the fiber surface can be increased when the plasma treated fiber material is contacted with an unsaturated compound that can be polymerized by free radical polymerization. This method has certain similarities to the present invention, but uses oxygen that is not equivalent to the steam plasma of the present invention, and uses unsaturated ethylenic monomers, which It is not equivalent to the invention epoxide.

US Pat. No. 4,705,7 to Kundiuger et al.
No. 20 relates to multilayer laminates. It shows a polyimide but does not show how to make the surface reactive as found in the present invention.

[0014]

The present invention provides one means of altering the surface properties of polymers used as dielectric insulating substrates, but leaving their overall properties unchanged. According to the invention, this method first functionalizes the surface of the substrate polymer, preferably polyimide, as a result of the treatment of contacting the surface with a steam plasma. The steam plasma treated reactive surface of the polymer is then contacted with a reactive component capable of being grafted thereon.

[0015]

DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS Stable surface properties that make it a desirable polymeric material for use in electronic packaging applications also include insufficient bond strength and bond durability and surface metallurgy. Problems exist because of infestation and the inability to inoculate. This very stable surface property can be altered by subjecting the substrate to a treatment with a low temperature plasma generated in a water vapor atmosphere under certain conditions.

According to the method of the present invention, the dielectric insulating polymer serving as a substrate is exposed to a water vapor plasma, which treatment renders the substrate, ie the surface of the polymer, susceptible to organic surface reactions by the grafting reagents. The physical and chemical properties of the polymer surface are effectively tailored while maintaining the desired overall properties.

More specifically, after treatment with a steam-containing plasma, the substrate surface contains increased amounts of hydroxyl and carboxyl functional groups formed on the surface during the steam plasma treatment. The resulting reactive functional groups are utilized as grafting sites. The grafting reagent used according to the invention is an epoxy,
It is composed of a compound selected from the group consisting of acid chlorides and isocyanates.

Generation of water vapor plasma has been generally known in the past. Plasma is typically generated by supplying a gas between a cathode and an anode with an RF electric field therebetween. The RF electric field dissociates the gas into charged and neutral free radical particles. In the steam plasma, water molecules can dissociate into hydroxyl ions and protons.
According to the invention, the substrate to be plasma treated is placed on either the cathode or the anode. Plasmas and methods of generating plasmas are described in detail in the article entitled "Plasma Technology" in the Supplement to the Encyclopedia of Chemical Technology , Third Edition. The contents of this article are incorporated herein by reference.

More particularly, the substrate polymer is processed at temperatures ranging from about ambient temperature (20 ° C. to about 25 ° C.) up to the glass transition temperature or melting point of the polymer being processed.

The preferred polymeric material for use in the present invention is polyimide, which has a glass transition temperature of greater than about 250 ° C. Other operating conditions used in the method of the present invention include pressure, which is high pressure, ie about 5
It can range from atmospheric pressure to ^sub- atmospheric pressures of about 10 ^-8 Torr, preferably in the range of about 50 to about 300 mTorr.

Electric power is direct current (DC), alternating current (AC),
Audio frequency (A.F.), intermediate frequency (I.F.)
F.), radio frequency (RF), microwave frequency, and the like.

The used power density, which is the amount of power per unit area, is in the range of about 10 ^-3 W / cm ³ to about 1000 W / cm ³ . The power density is preferably from about 10 ^-2 W / cm ³ to about 10 ¹ W / cm ³ .

The power used can come from any source of electrical energy, a particular example being a generator.

Treatment of the polymer body with steam plasma can be performed for a period of between about 0.1 minutes and about 1 hour or more.

The time of treatment depends on other operating conditions, including temperature, pressure and power, and this time the surface of the polymer is sufficiently reactive with hydroxyl and carboxyl functional groups to be grafted to the compound to be grafted. It is the time to treat the surface of the polymer until it becomes viscous.

Within the scope of the present invention, it is contemplated that the reaction of the grafting reactant will occur within a relatively short period of time after treating the surface of the polymer body with the steam plasma. If necessary, plasma treated polymer is approximately 8
It can be stored exposed to the atmosphere for days or longer.

The method of the present invention can be carried out in either an open or closed system. For example, when a closed system is used, the polymeric material to be treated is placed in a closed chamber and water vapor is passed into this chamber. The temperature and pressure of this room are maintained under predetermined operating conditions, which are as described above. Therefore, a high voltage electric field is applied between the two electrodes in this room. A discharge begins and a water vapor plasma consisting of ions, free radicals and unstable gas species is obtained.
The plasma is contacted with the surface of the polymer for a predetermined time for treatment, whereby the surface of the polymer is modified to form hydroxyl and carboxyl groups. At the end of the reaction time, the power is turned off and the treated polymer is removed.

It is also contemplated within the scope of the present invention to carry out the steam plasma treatment of the polymer in an open system, wherein the polymer to be treated is placed in an electric field between two electrodes and exposed to the electric field. During this time water vapor is passed over the surface of the polymer to make contact and the polymer is maintained at the desired operating temperature. After treating the polymer in the open system for a predetermined time, the polymer containing hydroxyl groups and carboxyl groups is ready for reaction with the reactive components shown below.

Preferred polymers are selected from the following: polyamides, polyesters, polyurethanes, polysiloxanes, phenolic resins, polysulfides, polyacetals, polyethylenes, polyisobutylenes, polyacrylonitriles, polyvinyl chlorides, polystyrenes, polymethylmethacrylates, polyvinylacetates. , Polytetrafluoroethylene, Polyisoprene, Polycarbonate, Polyether, Polyimide, Polybenzimidazole, Polybenzoxazole, Polybenzothiazole, Polyoxadiazole, Polytriazole, Polyquinoxalin, Polyimidazopyrrolone and aromatic components and vinyl and cyclobutane groups A copolymer with a component selected from the aromatic component and vinyl and cyclobutane. The over-flops, Babich said other 1989
US patent application Ser. No. 07 / 366,0 filed June 13, 2014
89, "Ga Filled Embedded Dielectric Structures, High Temperature Stable RIE Etch Stop Polymer Materials", Si, Ge, Ti, Zu and F.
including at least one of the groups such as e, the disclosure of which is incorporated herein by reference.

The more preferred polymers treated according to the present invention are polyaromatic polymers.

Further preferred polymers are polyaromatic polymers having a high glass transition temperature.

The most preferred polymer is a polyimide type polymer. Polyimide polymer is Encyclopedia
of Chemical Technology , 3rd Ed., Vol. 18, 70
It is described in the article entitled "Polyimide" on page 4 and is incorporated herein by reference for this description.

Generally, polyimides contain repeating units of the formula: where n is usually about 10,000 to about 100,
It is an integer indicating the number of repeating units for giving a molecular weight of 000.

[Chemical 1]

R is at least one tetravalent organic group selected from the group of those represented by the formula:

[Chemical 2]

R ₂ is a group consisting of a divalent residue of a C _{1 to} C ₄ aliphatic hydrocarbon, carbonyl, oxy, sulfo, sulfide, ether, siloxane, phosphine oxide, hexafluoroioisopropylidene and a sulfonyl group. Is selected from

R ₁ is at least one selected from the group consisting of aliphatic organic groups and those represented by the following formula:
Is a valent group, wherein R ₃ is a divalent organic group selected from the group consisting of R ₂ , silico and amino groups. Copolymers containing two or more R and / or R ₁ groups can also be used.

[Chemical 3]

Polyimides are commercially available from various suppliers in one of three forms: a) as a solution of a polyamic acid precursor (eg DuPont Pyralin); b) pre-. In imidized polyimide form (eg DuPont Kapton film); or c) as pre-imidized powder (eg Ciba-Geigy Matrimid 5218) or in solution (eg Ciba-Geigy probimide). Although the chemistries of commercially available polyimides are included in many of the above components, the preferred polymers used in accordance with the present invention are pyromellitic dianhydride (PMDA) and oxydianiline (ODA, also 4,4'-). (Also called diaminodiphenyl ether) based on both monomers. Another polymer preferred for use in accordance with the present invention is benzophenone tetracarboxylic dianhydride (BTDA).
And a polymer of ODA and / or 1,3-phenylenediamine and 3,3′-biphenylenediamine (PDA).

Polyimide film based on PMDA-ODA is manufactured by Allied Company under the trademark Apical ,
It is available from DuPont under the Kapton trademark. Films based on biphenyldianhydride-phenylenediamine (BPDA-PDA) are available as Upyrex from Ube and PIQ from Hitachi.
-Available as L100 . Other trade names for polyimides useful in accordance with the present invention include Durimide from Rogers and the following Pyralin series from DuPont: PI-2545, PI-254.
0, PI-2555, PI-2556, PI-256
3, PI-2560, PI-2525, PI-257
0, PI-2566, PI-2575, PI-257
6, PI-2574, PI-2580, PI-270
1, PI-2702, PI-2703, PI-2610
And PI-2611.

The polymer substrate is subjected to steam plasma treatment and then brought into contact with a compound selected from the group consisting of acid chloride, epoxy and isocyanate. Diglycidyl compounds are preferred specific examples of epoxies.

There is no particular factor necessary for the reaction with the compound described above to proceed between the compound described as being extremely reactive and the polymer surface.

Suitable acid chlorides which can be utilized according to the invention are any acid chlorides, especially malonyl dichloride, as well as para (cyano) benzoyl chloride and para (trifluoromethyl) benzoyl chloride.

When the epoxy resin is grafted to the substrate surface after the initial steam plasma treatment, it is allowed to crosslink the epoxy with a suitable anhydride reactant in the presence of a catalyst such as an amine. . Suitable anhydrides for the reaction include methyl nadic acid anhydride, hexahydrophthalic acid anhydride, methyltetrahydrophthalic acid anhydride, phthalic acid anhydride, maleic acid anhydride, nonenylsuccinic acid anhydride and succinic acid anhydride. Is.

The diglycidyl ether compound grafted on the surface of the substrate is used as an intermediate in the subsequent graft reaction. This makes it possible to virtually produce the desired surface layer with its properties and characteristics, while leaving the overall properties of the material on which the grafting is achieved.

The preferred isocyanate reactant is 2,4-
Tolylene diisocyanate, methylene bis (4-phenyl-isocyanate) and polymethylene polyphenyl isocyanate. This compound reacts with -OH groups to form urethane on the surface of the polymer substrate, eg: n (HO-R-OH) + n (OCN-R'-NCO) → HO- (R-OCONH-R ′ -HNCO-O) _n-1 -R-OCONH-R′NCO

Polymerization occurs on the surface of the substrate due to the reactivity of the isocyanate groups with various reactive groups such as --COOH and --NH ₂ as well as H ₂ O.

For example, water reacts with isocyanate to react with C
It produces O ₂ and an amine. R-NCO + H ₂ O → RNH ₂ + CO ₂ This amine further reacts with the isocyanate group. RNH ₂ + R'-NCO → R-NH-CO-NH-
R '

Also dimerized to a carbodiimide: 2R-NCO → RN = C = NR + CO ₂ and then trimerized:

[Chemical 4] Similarly, various other side reactions occur.

The compounds suitable for use in accordance with the present invention are essentially prepolymers, which react with the reactive surface of the steam plasma treated substrate, usually by addition of a catalyst or another reactant, It is like forming a reaction product that can undergo the second step polymerization.

This prepolymer is a struct set (st
ructoset) It is said to be a prepolymer. This second step reaction is usually different from the first step reaction. These polymers generally have greater control over the polymerization and cross-linking reactions and, very importantly, control over the structure of the product, and therefore have a high degree of advantage as coatings on the surface of substrates.

Structset prepolymers are low molecular weight polymers with various functional groups depending on the individual case. If the functional group is located at the end of the polymer chain, this prepolymer is a struct terminal (stru
ctoterminal) It is said to be a prepolymer. When the functional groups are located along the polymer chain, this prepolymer is a structopendant prepolymer. The reaction of the struct set prepolymer can be treated with a statistical approach to gelation by simply considering the prepolymer as a functionalized reactive agent.

There are two main classes of prepolymers that can be used according to the present invention. These are diol prepolymers and epoxy prepolymers.

Hydroxyl-terminated structual terminal polyether (H-OR-OH) _n and polyester H-
(OCOR'COOR) _n- OH is used exclusively as a prepolymer in polyurethane technology. Polyethers are commonly synthesized from ethylene and propylene oxide, and polyesters are synthesized from dibasic acids in the presence of excess diol.

These hydroxyl-terminated prepolymers react with excess diisocyanate to give isocyanate-terminated polymers, for example:

[Chemical 5] It can then be crosslinked in various ways. These isocyanate terminated prepolymers can react directly with steam plasma treated surfaces.

[0054]

[Chemical 6] Thus the addition of the diamine forms a urea bond by reaction with the isocyanate end groups, which in turn forms a biuret bond and crosslinks.

Epoxy prepolymers are usually formed from 2,2-bis (4-hydroxyphenyl) propane (called bisphenol A) and epiclohydrin.

[Chemical 7]

These are considered tract terminals or struct pendant prepolymers either because the cross-linking occurs through the epoxy end groups or through the hydroxyl groups. That is, when using anhydride (F-2) as the cross-linking agent, cross-linking occurs predominantly through the hydroxyl groups, and the epoxy prepolymer is considered a struct pendant prepolymer.

[Chemical 8] Phthalic anhydride is often used as a curing agent,
Other anhydrides, including maleic anhydride and pyromellitic anhydride, and the other anhydrides mentioned above may also be used in particular applications.

When a polyamine is used for cross-linking, this prepolymer is a struct terminal prepolymer. Crosslinking in this case involves base-catalyzed ring opening of the epoxy groups.

[Chemical 9] Both primary and secondary amines are used as crosslinkers. Since each N-H bond is reactive in this step, the primary and secondary amine functional groups have a functionality value (F) equal to 2 and 1, respectively. Ethylenetriamine (F = 5), Triethylenetetramine (F = 6)
Various amines are used as cross-linking agents, including and m-phenylenediamine (F = 4). Crosslinking with epoxide groups is also achieved by ring opening polymerization using tertiary amines as initiators.

Other epoxy compounds suitable for use as reactive compounds on the treated polymer surface are:

[Chemical 10] Where the average value of n is between about 0.2 and 1.6 and the epoxy functionality value is between about 2.2 and 3.6;

[Chemical 11] It has a theoretical functionality value of about 3.0;

[Chemical 12] Here, the average value of n is between about 0.7 and 3.4, and the epoxy functionality value is between about 2.7 and 5.4; a cycloaliphatic diepoxycarboxylate having the formula: Is.

[Chemical 13]

Further, 1,4-butanediol diglycidyl ether, triglycidyl isocyanurate and N,
N, N ', N'-tetraglycidyl-4,4'-methylenebisbenzenamine is also suitable.

Other suitable epoxidations useful in the present invention
The combination of Lee and NevilleHandbook of Epoxy Resiu
s, McGraw-Hill, 1982, shown in
Incorporated herein by reference. This
Governs the use of such compounds described herein
The only condition is that these are steam plasma treated surfaces
Is to be reactive with.

The following examples illustrate the method of the present invention.

Example 1 This example illustrates a method of treating a substrate according to the present invention.
MKS type 1150A-SP003-8 for introducing liquid vapor
An 8 Massflow meter was attached to the plasma chamber. This manifold consists of a liquid receiver and a regulating leak valve. A forced stop valve isolates the entire manifold from the plasma chamber. The manifold was wrapped with commercially available heating tape and the temperature was controlled by a variable transformer.

Typical plasma operating conditions are: Base pressure =
0.1-1 μtorr, electrode temperature about 25 ° C., plasma pressure about 100-300 mTorr, and RF output about 50 W.

In an attempt to verify the change of the surface during the steam plasma treatment, polystyrene (average molecular weight =
4,400,000, PDI = 1.06) was steam plasma treated and tested. The contact angle measurement of water using the stick-drop method (advancing angle 0.05 ml, receding angle 0.025 ml)
A remarkable change in the plasma treatment was clarified. The contact angles of untreated polystyrene are 90 ° advancing and 80 ° receding.
Was measured. The contact angle of polystyrene treated with steam plasma was measured to have an advancing angle of 3 ° and a receding angle of 1 ° or less. Transmission FTIR spectroscopy of polystyrene film etched in steam plasma to reduce the initial thickness from 400 A to a final thickness of 90 A
A new band of 1000cm ^-1 and 1750cm ^-1 that did not exist prior to exposure to the plasma has been shown. This is consistent with the idea of surface hydroxylation / carboxylation. Thus, after plasma treatment the substrate provides reactive sites that can be further reacted.

Example 2 A PMDA-ODA polyimide sheet was prepared and treated as described in Example 1 with steam plasma. Following treatment of the substrate with steam plasma, the number of available grafting sites on the surface was measured. The substrate was removed from the plasma chamber, cut into several pieces, and each piece was contacted with one of the following compounds:
Epoxy, acid chloride (malonyl dichloride), isocyanate and diglycidyl epoxy compounds.

Effective grafting in each case is fixation-
It is shown by observing the change in water droplet contact angle. After the steam plasma treatment, the contact angle of water is 19.5 ° ± 0.6 °
(Forward angle, 50 μl) and 3.5 ° ± 0.6 ° (receding angle, 2
5 μl). After reaction of this surface with malonyl dichloride, the angles were 62 ° ± 2 ° and 41 ° ± 2, respectively.
It was °.

Example 3 The substrate and method described in Example 2 above was repeated. To further demonstrate the surface reactivity, the chlorotrimethylsilane reagent was used in the stick-water drop contact angle evaluation. Water contact angle 66 ° ± 4 ° (advance angle, 50 μl) after draft and 3
9 ° ± 3 ° (receding angle, 25 μl) indicates successful grafting. This was confirmed by the appearance and XPS after the silicon peak was grafted with 101.1 eD.

Example 4 The substrate and method set forth in Example 2 above was followed, except that 4-cyanobenzoyl chloride was used as the grafting reagent. Successful grafting depends on contact angle and XP
Confirmed with S.

Example 5 The substrate and method set forth in Example 2 above was followed, except that 4- (trifluoromethyl) benzoyl chloride was used as the grafting reagent. Successful grafting was confirmed by contact angle and XPS.

Example 6 The steam plasma treatment of the polyimide sheet detailed in Example 2 was continued. Instead of using acid chloride, diglycidyl ether (Dow DER 667-bisphenol A type resin, epoxy equivalent 1600 to 2000) dissolved in methyl isobutyl ketone was used as a solvent for N, N-dimethylbenzylamine. Was used to react with the steam plasma treated surface. Successful grafting was noted by visual observation and was also confirmed by contact angle measurements and by copper plating using a conventional electroless copper plating bath with palladium inoculation.

The epoxy layer on the polyimide surface provides a substrate with desirable polyimide properties while at the same time providing the capability of an epoxy polymer, which Horkans et al., Ele.
ctrochem. Soc. 134 , 300 (1987) and Kim et al., IBM, R
It is activated for electroless copper deposition in the same manner as shown in es. Rev. , 28 , 697 (1984).

Example 7 The material prepared in Example 6 was used and crosslinked by reacting methyl nadic acid anhydride with N, N-dimethylbenzylamine catalyzed on a surface containing epoxy resin. .

Chain branching of the epoxy-faced polyimides prepared in the above examples gives products with epoxy surface properties combined with the excellent overall properties of polyimides, and based on what epoxy it is. It is a manufacturing method that can be implemented transparently depending on the method, and enables the production of a high-performance polyimide-based secondary level package.

The present invention has been described in detail above, but the present invention can be summarized and shown by the following embodiments. 1) exposing the dielectric polymer to water vapor plasma to form reactive sites on its surface; contacting the treated dielectric polymer surface with a substance capable of reacting with said reactive sites, A method of treating a dielectric polymer comprising grafting the material onto and forming a reaction product thereon. 2) The method according to item 1, wherein the substance is selected from the group consisting of an epoxy compound, an acid chloride, an isocyanate or a prepolymer of the above. 3) Dielectric polymer is polyamide, polyester, polyurethane, polysiloxane, phenol resin, polysulfide, polyacetal, polyethylene, polyisobutylene, polyacrylonitrile, polyvinyl chloride, polystyrene, polymethylmethacrylate, polyvinyl acetate, polytetrafluoroethylene, polyisoprene. , Polycarbonate, polyether, polyimide, polybenzimidazole, polybenzoxazole, polybenzothiazole, polyoxydiazole, polytriazole, polyquinoxaline, polyimidazopyrrolone and aromatic components and components selected from vinyl and cyclobutane groups. A copolymer containing, where the component is S
The method according to item 2 above, wherein the method is selected from the group consisting of i, Ge, Ti, Zn, and Fe.

4) The method according to item 2 above, wherein the dielectric polymer is a polyaromatic polymer. 5) The method according to item 4 above, wherein the polyaromatic polymer has a glass transition temperature of about 250 ° C. or higher. 6) The method according to the above item 3, wherein the dielectric polymer is polyimide. 7) The water vapor-containing plasma is at an electric field of about 10 ^-3 W / cm ³ to about 1000 W / cm ³ at a temperature from about ambient temperature to about the glass transition temperature of the polymer body to be treated. The method according to the preceding paragraph 3, which is generated under a pressure in the range of about 10 ⁻⁶ to about 5 atm for a period of about 0.1 minutes to about 1 hour. 8) The method according to item 7, wherein the substance is an epoxy resin. 9) The method according to item 8 above, wherein the epoxy resin is diglycidyl ether.

10) Epoxy resin is about 1600 to 20
The method of claim 8 wherein the epoxide equivalent of 00 is dissolved in methyl isobutyl ketone and the reaction occurs in the presence of an N, N-dimethylbenzylamine catalyst. 11) The method according to item 10 above, wherein the reaction product is further reacted by contacting with a cyclic anhydride. 12) The method according to item 11 above, wherein the reaction product is further reacted by contacting with methyl nadic acid anhydride. 13) The reaction product further reacts by contacting with hexahydrophthalic anhydride, the above 1
The method according to 1.

14) The method according to item 11 above, wherein the reaction product is further reacted by contacting with methylhexahydrophthalic anhydride. 15) The method according to item 11 above, wherein the reaction product is further reacted by contacting with phthalic anhydride. 16) The method according to item 11 above, wherein the reaction product is further reacted by contacting with maleic anhydride. 17) The method according to item 11 above, wherein the reaction product is further reacted by contacting it with nonenylsuccinic anhydride. 18) The method according to item 11, wherein the reaction product is further reacted by contacting with succinic anhydride.

19) The method according to item 7 above, wherein the substance is an acid chloride. 20) The above-mentioned item 19, wherein the substance is malonyl dichloride
The method described in. 21) The method according to item 19 above, wherein the substance is 4- (cyano) benzoyl chloride. 22) The method according to the above item 19, wherein the substance is 4- (trifluoromethyl) benzoyl chloride. 23) The method according to item 7 above, wherein the substance is isocyanate. 24) The method according to the above item 23, wherein the substance is 2,4-tolylene diisocyanate. 25) The method according to the above item 23, wherein the substance is methylenebis (4-phenylisocyanate).

26) The method according to item 23 above, wherein the substance is polyphenyl isocyanate. 27) The method according to item 2 above, wherein the substance is a prepolymer, that is, a tract set prepolymer. 28) The method according to item 27 above, wherein the tract set prepolymer is a struct terminal prepolymer. 29) The method according to item 27 above, wherein the tract set prepolymer is a tract pendant prepolymer. 30) The method according to item 7 above, wherein the substance has the following formula.

[Chemical 14]

31) The above item 7 wherein the substance has the following formula:
The method described in.

[Chemical 15] Here, the average value of n is between about 0.2 and 1.6, and the epoxy functionality value is between about 2.2 and 3.6. 32) The method according to the above item 7, wherein the substance is 1,4-butanediol diglycidyl ether. 33) The method according to item 7 above, wherein the substance is triglycidyl isocyanurate. 34) The substance is N, N, N ', N'-tetraglycidyl-
4,7 ', which is 4,4'-methylenebisbenzenamine.
The method described in. 35) The method according to item 7 above, wherein the substance is of the following formula and has a theoretical functionality value of about 3.0.

[Chemical 16]

36) The above item 7 wherein the substance has the following formula:
The method described in.

[Chemical 17] Here, the average value of n is between about 0.7 and 3.4, and the epoxy functionality value is between about 2.7 and 5.4. 37) The method according to the preceding item 7, wherein the substance is an alicyclic diepoxycarboxylate having the following formula.

[Chemical 18] 38) The method according to the above item 7, wherein the polymer is polyimide. 39) The method according to the above item 38, wherein the polyimide is a reaction product of PMDA and ODA. 40) The acid chloride is malonyl dichloride,
Item 39. The method according to Item 39. 41) The method described in 10 above, wherein the polymer is polyimide. 42) The method according to the above item 38, wherein the polyimide is a reaction product of BPDA and PDA.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08G 83/00 NUW 85/00 NVA C08J 7/18 7310-4F H01L 23/02 (72) Inventor Charles Robert Davis New York, USA 13760. End cot. Hill Avenyu 940 (72) Inventor Ronald Dane Goldbladto New York, USA 10573. Librutsk. South Ritsuji Street 242 (72) Inventor Richard Ronald Thomas New York, USA 12524. Fish kill. Ivy coat 7A (56) Reference JP-A-59-43010 (JP, A) JP-A-62-54734 (JP, A) JP-A-62-50338 (JP, A) US Pat. No. 4131691 (US, A)

Claims (2)

[Claims] 1. A substance capable of exposing a dielectric polymer to water vapor plasma to form reactive sites on its surface; a substance capable of reacting the treated dielectric polymer surface with the reactive site. A method of treating a dielectric polymer comprising contacting with an epoxy compound, an acid chloride, an isocyanate or a prepolymer of the foregoing, grafting the material thereon and forming a reaction product. . 2. The water vapor-containing plasma is at a temperature from about ambient temperature to about the glass transition temperature of the polymer body to be treated, from 10 ⁻³ W / cm ^{3 to} 1000 W / c.
The method according to claim 1, which is generated in the electric field of m ³ electric power under a pressure in the range of 10 ^{−6 to} 5 atmospheres for a range of 0.1 minutes to 1 hour.